Thermodynamic and physicochemical properties of binary mixtures of sulfolane with ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol systems at 303.15 K

doi:10.1016/j.fluid.2007.09.009

Fluid Phase Equilibria

Volume 262, Issues 1–2, 15 December 2007, Pages 244-250

https://doi.org/10.1016/j.fluid.2007.09.009 Get rights and content

Abstract

Densities and relative permittivities, at T = 303.15 K, in the binary mixtures of sulfolane with ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol have been measured as a function of composition. From the experimental data excess molar volumes and the deviations in the relative permittivity from a mole fraction average have been calculated. The results are discussed in terms of intermolecular interactions and structure of studied binary mixtures.

Introduction

This paper is a continuation of our studies on the thermodynamic and structural properties of some mixtures of glycols with different solvents [1], [2], [3]. In the present work, we have measured the density (ρ) and relative permittivity (ɛ) over the entire composition range, at 303.15 K, for binary mixtures of sulfolane (SLF) with ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG), and tetraethylene glycol (TETRAEG).

Sulfolane is a typical dipolar aprotic solvent with a low donor number of 14.81 and a large dipole moment and relative permittivity in the liquid phase (μ = 4.8 D; ɛ = 43.39 [4]). The proton basicity of sulfolane is much lower than that of water or even acetonitrile, as shown by its pK_a(SH⁺) value of −12.9, as compared to ca. −9.5 for acetonitrile [4]. The inert role of sulfolane as solvent and the above-cited regular behavior of its solutions were ascribed to the low accessibility of its dipole because of the steric hindrance of the globular molecule, which prevents remarkable interactions of any kind [5], [6], [7], [8], [9], [10]. Ethylene glycols are very interesting class of solvents, due to the presence of the oxy and hydroxyl groups in the same molecule, which allow self-association via intra- and intermolecular hydrogen bonds [11], [12], [13], [14], [15], [16]. The formation of intramolecular hydrogen bonds in the liquid glycols is more favourable when the molecules of these solvents are in the gauche conformations [11], [12], [13]. These solvents have found a wide variety of applications in the petroleum, cosmetics, textile, pharmaceutical, and the other industries.

Taking into account these literature structural informations, the aim of this work is to provide a set of data in order to assess the influence of the size and shape of ethyleneglycols on thermodynamic properties of mixtures when we pass from a molecule with one ( double bond SO₂) functional group to a molecule with several (–O– and –OH) functional groups. Also, an attempt has been made to interpret the results in terms of the molecular interactions between ethylene glycols and sulfolane.

In this paper, from experimental results, the excess molar volumes (V^E) and deviation of relative permittivity (Δɛ), at T = 303.15 K, have been calculated. These quantities have been fitted to the Redlich–Kister equation [17], to obtain the binary coefficients and standard deviations. Furthermore, the experimental results have been used to describe the nature of intermolecular interactions.

Section snippets

Materials

The following materials with mole fraction purity as stated were used: sulfolane (Aldrich, purum, GC ≥ 0.98 mole fraction), ethylene glycol (Fluka, Switzerland, puriss. anhydrous, GC > 0.99 mole fraction), diethylene glycol (Fluka, Switzerland, puriss. p.a., GC ≥ 0.995 mole fraction), triethylene glycol (Fluka, Switzerland, puriss. anhydrous, GC > 0.99 mole fraction), and tetraethylene glycol (Fluka, Switzerland, purum, GC ≥ 0.99 mole fraction). All glycols were further purified by the methods described

Results and discussion

The experimental densities (ρ) and relative permittivities (ɛ) obtained from the measurements of the pure solvents and for the binary mixtures at 303.15 K are summarized in Table 2, Table 3.

The variations of the density and relative permittivity with binary composition were studied by using the following equations [23], [25]: $ρ (x_{1}) = \sum_{j = 0}^{4} b_{j} x_{1}^{j}$ and $ln ε (x_{1}) = \sum_{j = 0}^{4} β_{j} x_{1}^{j}$ which could be fitted to the experimental data at 303.15 K using a least-squares method. The b_j and β_j coefficients of this fitting

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Densities (ρ), speeds of sound (u) and viscosities (η) for binary mixtures of {water + ethanol, or + ethylene glycol (EG), or + diethylene glycol (DEG), or + triethylene glycol (TEG), or + polyethylene glycol (PEG) 200, or + polyethylene glycol (PEG) 300, or + polyethylene glycol (PEG) 400, or + polyethylene glycol (PEG) 600, or + glycerol} have been determined as a function of composition at T = (293.15, 298.15, 303.15 and 308.15 K) and atmospheric pressure. From these results, excess molar volume ( $V_{m}^{E}$ ), deviation in isentropic compressibility (Δκ_S), deviation in viscosity (Δη), and excess Gibbs energy of activation for viscous flow (ΔG^∗E) were calculated and fitted by the Myers-Scott equation, as a function of mole fraction. Values of $V_{m}^{E}$ and Δκ_S were negative over the entire composition range for all mixtures studied. The values of Δη were negative for the systems containing ethylene glycol and glycerol and positive for the systems containing ethanol, PEG 400 and PEG 600. For other systems, the deviation of viscosity presented an S-shape, with negative values at high water concentration. For all mixtures studied, the values of ΔG^∗E were positive over the entire composition range. The results obtained were discussed in terms of structural effects and intermolecular interactions between like and unlike molecules.
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The experimental densities of sulfolane (TMS) + 1, 5-pentanediol at 293.15–313.15 K and refractive index at 298.15–308.15 K were reported and expressed by mole fraction of 1, 5-pentanediol. The experimental data of density were used to calculate the excess molar volume, partial molar volume, excess partial molar volume, apparent molar volume, partial molar volumes at infinite dilution, apparent molar volumes at infinite dilution, coefficient of thermal expansion, and excess coefficient of thermal expansion. The deviations in refractive index data were calculated by the Reis equation. Also, the deviations in refractive index and the excess molar volume were fitted using the Redlich-Kister polynomial equation to derive the binary adjustable parameters and standard errors. To probe the interactions and to correlate the excess molar volumes of the examined mixtures, the Prigogine − Flory − Patterson (PFP) theory has been used. The experimental values of refractive indices were examined with two semi-empirical equations of Heller and Edward models. To evaluate the validity of the proposed equations, comparisons were made among the experimental and predicted data. The results are discussed in terms of the intermolecular interactions.
Ultrasonic, DFT and FT-IR studies on hydrogen bonding interactions in aqueous solutions of diethylene glycol
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The density, viscosity and ultrasonic velocity measurements were carried out in aqueous diethylene glycol (DEG) solutions at different concentrations and temperatures to illustrate the hydrogen bonding interactions of DEG with water. The main acoustic parameters such as isentropic compressibility (β_s), acoustic impedance (Z), hydration number (H_n), intermolecular free length (L_f), classical sound absorption (α/f²)_class and shear relaxation time (τ) were calculated based on the experimentally measured values. These parameters have been utilized to study the solute–solvent interactions in aqueous DEG solutions. Further, these results suggest that the clusters of likely complex DEG molecule form hydrogen bonding with five water molecules in aqueous solution. The quantum chemical calculations were also performed to study the hydrogen bonding interactions between DEG in g⁻g⁺t–tg⁻t conformation and five water molecules. Computations have been done by DFT method at B3LYP/6-311 + g(d,p) level of theory to study the equilibrium structure of DEG monomer in gas phase, DEG–(water)₅ interacting complex in gas and solvation phases and the vibrational frequency shift due to formation of intermolecular hydrogen bonding. The solvation phase study was carried out using Onsager's reaction field model in water solvent. The computed and scaled vibrational frequencies are in good agreement with the main features of the experimental spectrum when five water molecules are considered explicitly with DEG in g⁻g⁺t–tg⁻t conformation. The parameters such as optimization energy (E_total), hydrogen bond length and dipole moment (μ_m) of the interacting complex are also presented and discussed within the light of solute–solvent interactions.
Studies on intermolecular interactions in sulfolane + alkoxyethanol binary mixtures by speed of sound and <sup>1</sup>H NMR measurements at T = 303.15 K
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Speed of sound, at 303.15 K, and ¹H NMR spectra, at 303 K, in binary mixtures of sulfolane (SU) with 2-methoxyethanol (ME), 2-ethoxyethanol (EE), 2-propoxyethanol (PE) and 2-butoxyethanol (BE) have been measured over the whole composition range under atmospheric pressure. From the experimental data the deviations in speed of sound (Δu), excesses of isentropic compatibility (κ_s^E), and the deviations in chemical shifts (Δδ) from a mole fraction average have been calculated. The results are discussed in terms of intermolecular interactions and structure of studied binary mixtures.

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Thermodynamic and physicochemical properties of binary mixtures of sulfolane with ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol systems at 303.15 K

Abstract

Introduction

Section snippets

Materials

Results and discussion

J. Chem. Thermodyn.

J. Chem. Thermodyn.

J. Mol. Liq.

Fluid Phase Equilibr.

Thermochim. Acta

J. Chem. Thermodyn.

Chem. Thermodyn.

Colloid Polym. Sci.

J. Mol. Spectrosc.

J. Polym. Sci. A

J. Chem. Eng. Data

Anal. Chim. Acta

Pure Appl. Chem.

J. Chem. Eng. Data

Z. Naturforsch.

Fluid Phase Equilibr.

Makromol. Chem.

J. Phys. Chem.

J. Appl. Polym. Sci.

Thermochim. Acta